Dianhydride curing agent for epoxy resins



United States Patent 3,336,260 DIANHYDRIDE CURING AGENT FOR EPOXY RESINS 6 Claims. (Cl. 260-47) This is a division of application Ser. No. 86,308 filed Feb. 1, 1961.

This invention relates to the curing of epoxy resin compositions. More particularly it relates to thermosetting epoxide resin systems and to processes for making them. It is especially directed to novel thermosetting epoxy resin/dianhydride systems which are characterized by high heat distortion temperature characteristics.

Epoxy resins comprise a class of resins usually formed as the result of the reaction of an epihalohydrin and a phenol or al-iphatic'polyol. These resins are characterized by the inclusion within their structure of epoxide groups which permit the resin units to be homopolymerized with the aid of catalysts or copolymerized with the aid of hardening agents such as polyamines, polyamides, and organic acid anhydrides.

The epoxy resins by virtue of their excellent combination of physical, chemical and electrical properties have become an important class of plastic materials. They are used in an increasingly large volume in such varied fields as coatings, molding and encapsulation compounds, binders for laminates, adhesives and electrical insulation. In many such instances, the resulting resins are subjected to elevated temperatures. Unfortunately, the excellent properties of these resins at room temperature or slightly above, progressively deteriorate at or near the softening point of the resin.

Although in many instances epoxy resin compositions can be cured at room temperature, in order to produce a material possessing optimum properties and especially increased softening point, external heat and curing agents are required.

The prior art teaches the use of a variety of curing agents, each of which gives rise to a finished res-in of widely different properties. Of the two main classes of curing agents, amines and acid anhydrides, the latter are characterized by curing epoxide resins with the evolution of a relatively small amount of heat, and give tough cured resins having relatively good heat stability.-

More recently, dianhydrides have been suggested as curing agents on the theory that the extra functionality of these agents would, by increasing the density of cross linking within the polymer, give rise to cured polymers which were tougher and possessed even better heat stability. Unfortunately, the available tetracarboxylic dianhydrides are few in number and those which are available, are relatively costly, high melting, i.e. they are solid even at the usual formulating temperature, and possess poor compatibility in the resin system. The defect of high melting point can be overcome by the admixture with the dianhydride of a monoanhydride, such as phthalic acid anhydride to produce a mixture of satisfactory melting point. The mixture however, though lower melting and more compatible, dilutes and hence reduces the improvements gained by the dianhydride.

It is therefore an object of this invention to provide an epoxy resin/anhydride cured system which is distinguished by a high heat distortion temperature.

An ancillary object is to provide a dianhydride epoxy curing agent which is liquid at normal working temperatures and compatible with the uncured epoxy resin.

3,336,260 Patented Aug. 15, 1967 Another object is to devise processes for the formulation of epoxy resin/dianhydride systems which possess satisfactory pot life and when cured are distinguished by a high heat distortion temperature.

In accordance with the present invention, it has been found that dianhydrides obtained by reacting a polyalkylbenzene, in which each alkyl group contains 2 to 6 carbon atoms, with maleic acid anhydride, make excellent curing agents. for epoxy resins. In particular, the addition to an epoxy resin mass of an effective amount of phenylene-bis- (3-butane-1,2-dicarboxylic acid anhydride) of structural formula shown at top of column 4, results in a resin mass having a surprisingly high heat-distortion temperature. In addition, the cured resins possess, in general, excellent adhesion to metal surfaces, low shrinkage during cure, good electrical and mechanical properties and excellent stability under varying conditions of humidity and temperature.

Among the reactions theoretically possible when a dianhydride such as phenylene-bis-(3-butane-1,2-dicarboxylic acid anhydride) is used as a curing agent of epoxy resins in accordance with this invention are the following:

(1) The reaction between the anhydride group and the secondary hydroxyl group in the polymer chain to form an ester linkage and a free carboxyl:

O (3 o lorr 0 l-o( i o I ii n0o (2) The reaction between the resulting carboxyl groups and an epoxide group of the resin to give another ester linkage and a free hydroxyl:

I (3) The self-condensation, which probably is catalyzed by the carboxyl groups formed in reaction (1), between hydroxyl and epoxide groups of the polymer:

OH CEfiCH- OCH:(]3H

O OH Since theoretically one anhydride moiety is sufficient to react completely with one oxirane group and with the the other hand, resins with superior properties are ob- 1 Anhydride equivalent is defined as the weight of anhydride which contains 1 gram chemical equivalent of anhydride groups (CO)2O.

2 The epoxy equivalent 1s defined as the weight of epoxy resin in grams which contains 1 gram chemical equivalent of epoxy (oxirane) group. It is determined by reacting a known quantity of epoxy resin with a known quantity of hydrochloric acid and back titrating the excess acid to determine the amount consumed. Since one mole of acid reacts with each epoxy group according to I I I each mol of acid consumed is equivalent to one epoxy group.

tained when the A/E ratio exceeds one. Accordingly, we have found it feasible to use as an effective amount at least 0.6 anhydride equivalent per epoxide equivalents to obtain adequate curing. We prefer to use between 0.85 and 1.5 anhydride equivalents per epoxy equivalent, and especially between 1.00 and 1.25 anhydride equivalents per epoxy equivalent should be used. The use of still larger amounts of anhydride is operative but may be wasteful.

Further, the postcure temperature and time of the reaction can be varied over a considerable range. Because of its relatively moderate reactivity and extraordinary compatibility, phenylene bis-(S-butane-1,2-dicarboxylic acid anhydride) is particularly easily incorporated into heated epoxy liquids. The postcuring of the resin, during which the major amount of the cross linking operation is effected, as indicated by the achievement of the maximum heat distortion temperature of the cured resins, is conveniently carried out at from about 150 to 250 C. for from 10-24 hours. A temperature of at least about 170 C. is preferred; and generally, a temperature of about 200 C. maintained for about 20-24 hours will result in a cured resin having a maximum heat distortion temperature.

The novel dianhydride curing agents of this invention can be prepared by condensing a polyalkyl benzene, preferably a technical mixture of the several isomeric forms of the polyalkyl benzene, with two molecular equivalents of maleic acid anhydride in the presence of a free radical catalyst, such as benzoyl peroxide, a,ot-azo-diisobutyronitrile and the like.

Typical peroxy catalysts other than benzoyl peroxide which can be used for this purpose include organic peroxides such as acetyl peroxide, lauryl peroxide, stearyl peroxide, acetone peroxide, tert.-butyl hydroperoxide, ditert.-butylperoxide, di-tert.butyl diperphthalate, tert.- butyl perbenzoate, cumene hydroperoxide, hydroxy cyclohexyl hydroperoxide, and the like; inorganic peroxide such as hydrogen peroxide; peroxy acids such as peracetic acid; etc. We have found that other free radical catalysts can be used instead of peroxy catalysts for producing our dianhydrides, e.g. a,a-azodiisobutyronitrile as above stated; other azo compounds such as phenylazotriphenylmethane or azodibenzoyl; triazenes (i.e. diazoamino compounds) such as 1 phenyl-3,S-dimethyltriazene; nitrosoacylarylamines such as N-nitrosoacetanilide; and nitrosoacylalkylamines such as N-benzyl-N-nitrosoacetamide. Still other nitrogen-containing compounds can be used under relatively severe heating conditions, e.g. oximes such as acetone oxime, butyraldoxime, cyclohexanone oxime, etc.; and other types such as organometallic compounds, e.g. tetraethyl lead, are also usable.

Although the amount of catalyst used can vary considerably, the preferred amount ranges from 2 to 10% of the maleic acid anhydride used, especially from 5 to 7%.

We have found that a very high ratio of dianhydrides to monoanhydrides is obtained by adding a solution of catalyst in slightly more than 1 mol portion of polyalkylbenzene, in small increments and over an extended period, to a mixture of at least 2 mol portions of maleic anhydride and about 1 mole portion of polyalkylbenzene. Mixtures containing more than 95% dianhydride and 5% monoanhydride have been obtained in this manner. Surprisingly, however, the most satisfactory products for our purpose are obtained by use of a relatively large mol ratio, such as about 10:1 of polyalkylbenzenezmaleic anhydride in the initial reaction mixture, to which is added maleic anhydride and a solution of catalyst in polyalkylbenzene, the ultimate maleic anhydridezpolyalkylbenzene mol ratio being about 0.5:1-1z1.

Temperatures to be employed in producing our dianhydrides are dependent on other conditions, especially catalyst proportion and stability, and are generally at least sufficient to assure presence of maleic anhydride rather than maleic acid, ie at least about 135 C. Suitably the temperature can be as high as allowed by the boiling point of the reaction mixture at the prevailing pressure, which usually willl be atmospheric or higher. Thus with readily decomposable catalysts suitable temperatures lie from about 135 C. to the atmospheric boiling point of the reaction mixture; and with more stable catalysts higher temperatures can be used, such as 200300 C., under pressures at least suflicient to maintain a liquid phase.

The synthesis can be represented by the following equation:

Other polyalkylbenzenes which can be employed in producing the subject dianhydrides, besides the diethylbenzenes, are primary and secondary dipropylbenzenes, the primary and secondary dibutylbenzenes, the primary and secondary dihexylbenzenes; and C -C alkyl, nuclearly substituted, homologues of the foregoing. The primary dialkylbenzenes are preferred as being more reactive than the secondary isomers. The resulting dianhydrides in accordance with this invention have the structural formula:

C-CH-C I R /0 0112-0 w I s 5 -OHC I t o CH2C\ O inwhich R RI! /C and /C are alkylidene radicals each containing 2 to 6 carbon atoms and R represents 4 nuclear substituents each selected from the group consisting of hydrogen and C -C alkyl radicals. In the dianhydrides obtained from the preferred polyalkylbenzenes, viz. from primary dialkylbenzenes, all the substituents represented in the above formula by R, R", and R are hydrogen atoms.

As an illustrative embodiment of the preparation of a dianhydride curing agent of this invention, the following example is given in which the parts are by weight and the temperatures are given in degrees centigrade.

Example A A mixture of 196 parts of maleic anhydride and parts of diethylbenzene was heated to -145 C. A solution of 11 parts of benzoyl peroxide in 154 parts of diethylbenzene was added dropwise during 1% hours while agitating the reaction mixture at 135l45 C. The agitated reaction mass was further heated for 1 hour at 135145 C., then cooled and distilled in vacuo. The following fractions were collected:

to -150 C./1 mm.--116.7 parts=unreacted diethylbenzene, and maleic anhydride.

5 145200 C./1 mm.-10 parts=monoanhydride (2% yield). residue303.7 parts==dianhydride product92% yield based on maleic anhydride (assuming that product is all the desired anhydride) The neutral equivalent of the dianhydride product thus obtained was 162 (theory=165), indicating a product of good purity. The NE value of 162, which is slightly less than 165 for theory, suggests that the dianhydride product contains (a) no monoanhydride and (b) a small amount of polyanhydride of unknown constitution formed as a by-product in the reaction.

A particularly excellent product, based on its curing activity with epoxy resin, was obtained as follows:

Example B Diethylbenzene (460 parts, 3.4 mols) and maleic anhydride (30 parts, 0.3 mol) were heated in a nitrogen atmosphere to 165 -170 C. The mixture was agitated as maleic anhydride (558 parts, 5.7 mols) and a solution of benzoyl peroxide (33 parts, 0.135 mol) in diethylbenzene (472 parts, 3.5 mols) were added dropwise in separate streams to the agitated mass. The maleic anhydride was added in 60-75 minutes and the catalyst solution in 95- 110 minutes. Thereafter the mixture was agitated at 165 170 C. for /2-1 hour. I

The mass was distilled in vacuo. The following frac tions were collected:

to 145-155 C./1-2 mm.unchanged maleic anhydride and diethylbenzene. 145170 C./0.2-l mm.monoanhydride505 parts.

wherein is an alkylidene radical containing 2 to 6 carbon atoms,

-R' represents 4 nuclear substituents each selected from the group consisting of hydrogen and C -C alkyl radicals, and R represents an alkyl radical containing 2 to 6 carbon atoms. The following example illustrates a method of doing this.

Example C (1) PREPARATION OF MONOA-NHYDRIDE I-N PRESENCE a,a.'-AZO-DIISOBUTYRONITRILE A mixture consisting of 39.2 parts (0.4 mol) of maleic anhydride and 495 parts (3.7 mols) of diethylbenzene was heated to 145 to 150. Thereafter 5.8 parts (0.0354 mol) of a,a'-azodiisobutyronitrile dissolved in 188 parts (1.4 mol) of diethylbenzene were added dropwise over a 2 hour period, during which and at half hour intervals, 3 portions of 19.6 parts (0.2 mol) each of maleic anhydride were added. The reaction mass was heated at 138 to 166 in 1 /2 hours after the reactants had been charged.

The reaction mixture was then stripped of unreacted diethylbenzene under a vacuum of about 5 mm., which was reduced, as the forward flow decreased, to about 0.5 mm. The temperature was then gradually increased. A fraction distilling for the most part at 153 to 156/0.4 to 0.5 mm. and amounting to 155 parts was collected. This frac tion had an index of refraction N =1.5243. A second fraction, amounting to 7.0 parts distilled at 155 to 157/ 0.5 mm. (N =1.5260).

Neutral equivalent of the first fraction (in methanol) found: 229.8, 231.6 (calculated for monoanhydride 232). A residue of 53 parts remained in the distillation flask.

(2) REACTION OF MONOANHYDRIDE WITH MALEIC ANHYDRIDE A mixture of 215 parts (0.925 mol) of the monoanhydride product prepared as described in (1) above and 9.8 parts (0.1 mol) of maleic anhydride was heated to between 140 and 150 and 1.46 parts (0.0089 mol) of a,a'-azodiisobutyronitrile suspended in 75 parts (0.323 mol) of the monoanhydride were added dropwise inabout 2 hours. After about 20 minutes and at 20 minute intervals thereafter 3 portions of 4.9 parts (0.05 mol) each of maleic anhydride were charged to the mixture. The mass was heated for 4 hour after the addition of catalyst slurry was complete.

The mass was distilled in vacuum whereby 207 parts of monoanhydride were recovered (boiling point 142 to 154/0.3 to 0.5 mm.). The residue, amounting to 58 parts, had a neutral equivalent of 168.7 in methanol. It was identified as phenylene-bis(3-butane-1,2-dicarboxylic anhydride), which has calculated neutral equivalent of 165. The yield was about 70.3% of theory based on the amount of monoanhydride consumed.

The synthesis can be represented by the following equation:

CH3CH2 I C-CH-GH C-CHz A solution of 22.5 parts of phenylene-bis-(3-butane- 1,2-dicarboxylic acid anhydride) in 25 parts of a standard commercially available epoxy resin (Epon 828a product of Shell Development Corporation-being an epichlorohydrin-bis phenol-A liquid resin, having an average molecular weight of between 350 and 400 and an epoxy value 1 of 0.52) was prepared at 70 to To the solution, 0.36 part of benzyldimethylamine (0.02 mol/epoxy equivalent) was added and the mixture stirred until uniform. The solution was poured into a 7" x /2 x /2" brass mold, coated with a silicone mold release agent (Dow Corning DC-20). One end of the mold was closed with a Silastic 51 rubber plug. The resinous compositions were precured at 80 for two hours and postcured at 200 for 20 hours. The heat distortion temperature (HDT) of the cured resin so obtained as deter- Epoxy value (oxirane value) represents the number of epoxy groups contained in grams of epoxy resin. The epoxy value divided into 100 gives the epoxy equivalent.

Thus, a resin having an epoxy value of 0.50 has an epoxy equivalent of 200.

7 mined by standard ASTM method D648-56 (10 mils deflection) was 184.

EXAMPLE 2 columns headed PBDAA of Table I below. For comparison, similar resin systems cured with phthalic acid anhydride were prepared and heat-distortion temperatures were determined as set out in the columns headed By essentially the procedure of Example 1, an epoxy PAA f bl 1 b l resin having an HDT i 192 was Prepared g l T able I. Formulation and curing schedule t ,2 i fz g i g ens bis (3 bu ane 1 lcarboxy 1c Epoxy Resin Epon 828 (epoxy value:0.52). 20 0 parts of Epon 828 Catalyst Benzyldimethylamine.

4 Catal st concentration 0.02 mol/e ox e uivalent. 0.28 art of benz ldimeth lamine y p y q P y y Precure schedule 2-3 hours at 80.

EXAMPLE 3 Postcure schedule hours at the indicated In an analogous manner, other commercially available temperature.

HDT

Postcure A/E=0. s5 A/E=1. 05 A/E=1. A/E=1. 45 Tertnperame PBDAA PAA PBDAA PAA PBDAA PAA PBDAA 170 131 135 15s. 5 140 isi. 5 127 173 200 139 129 184. 0 152 192. 0 118 167 230 148 130 170. 0 147 17s. 0

epoxy resins can be advantageously cured with the dian- These data indicate that at an A/E of at least 1.05 hydride agent of this invention. Thus using in the proand at a postcure temperature of at least about 170, cedure of Example 1 above: epoxy resin systems cured with phenylene-bis-(3-butane- 1,2-dicarboxylic acid anhydride) are markedly superior 5 g g dg1eny1ene'bls'(3'butane'12 dlcarboxyhc with respect to HDT to those systems cured with phthalic 20.0 parts of Bakelite ERL 3794 (epoxy value=0.55) and anhydnd- 0.297 part of benzyldimethylamine EXAMPLE 7 and curing as in Example 1 above, resulted in a resin The effect on HDT of phenylene-bis-(3-butane-1,2-dihaving an HDT of 195. carboxylic acid anhydride) as a curing agent for various commencially available epoxy resins is indicated by the EXAMPLE 4 1 data in Table 11 at A/E of 1.05 and 1.25.

When epoxylated Novolac X2638.3, an experimenta product of DOW Chemical having an epoxy value of Table II.F0rmulatz0n and curmg schedule 0.556, was used instead of the Bakelite ERL 3794, and Epoxy resin As indicated.

22.9 parts instead of 22.6 parts of dianhydride were used, Catalyst Benzyldimethylamine.

other variables being the same as in Example 3 above, Catalyst concentration 0.02 mol/epoxy equivalent.

the HDT of the cured resin was above 212, the tempera- Precure schedule 2 hours at 80.

ture maximum of the test apparatus. Postcure schedule 20 hours at 200.

EXAMPLE 5 HDT Pyromellitic dianhydride has been proposed as an AIE=105 A/E 125 epoxy curing agent. This agent, however, is incompatible (degrees) (de iee's) with many epoxy resins such as Epon 828 (epoxy value 0.52) and, being a relatively high melting solid, is diffi- Araldite 6020 17 170 cult to incorporate and use. These defects can be over- 13 Rel 182 180 i Rez 515 108 103 come to some extent by admixture with other polycar- Bake1iteERL3794i 178 195 boxylic acid anhydrides, such as phthalic acid anhydride, in order to increase compatibility and lower the melting Novolac X issfzii l ffjfijl f: 210 210 point thus increasing the ease of incorporation. Phenylene-bis-(S-butane-1,2-dicarboxylic acid anhydride) can also be used in admixture with pyromellitic dianhydride LEGEND Vise M7301? as a curing agent for epoxy resins to produce resins characterized by high HDT- b b 1 2 d b 1 zgroguc'g o; Ciba, 1pc epoxy value 9.478. 28,080-40,00g

16.1 parts of phenyleneis-(3- utaneicar oxy ic p y va u 1,0 0-20,00

1 acid anhydride) and 3.5 parts of pyromellitic dianhydride zgigg gg t g iiia r gar bfiiief g iiy gaiitie gig. 2 222 3 were melted together to form a homogeneous mixture fi emlcaiepoxy Va 11C i 00 o o Oh i, i 0.38 4, which softens at 55 and becomes fluid at 90 This pigciggtigDoiv ohefit,tgiiiigvhiu ohsfi,and being 0 000 90 000 8116 OX1 1Z9 urea- OInl 6 G n. mixture was added to zqparts of Epon 828.and .Warmed 5 l roduct of Union larbi de, gbxy value 0.715 and until a tan opaque solution resulted. To this fluid mass, having the probable chemical formula 0.28 part of benzyldimethylamine was added and the resin cured by the procedure of Example 1 above. The cured Giro-f) resin had a HDT value greater than 212, the maximum O temperature measurable in the available test apparatus. 0 0

EXAMPLE 6 The effect of postcure temperature and of variation EX A PLE of the anhydride equivalent per epoxy equivalent (A/E) M 8 on the heat-distortion temperature of epoxy resin systems Whe n the F' Y Tesln p 828 Was ulat d and was determined with resins cured with phenylene-bis-(3- Cu 1n t manner des ribed in Example 7 in the presbutane-1,2 dicarboxylic acid anhydride) as set out in the ence of the dianhydride obtained by reacting diisopropylbenzene with maleic acid in the manner described in Example A, its heat distortion temperature for an A/E value of 1.05 was 155 and at an A/E value of 1.25 its heat distortion temperature was found to be 154.

EXAMPLE 9 When Epoxide 201 was formulated and cured in the manner described in Example 7 in the presence of the dianhydride obtained by reacting diisopropyl-benzene with maleic acid in the manner described in Example A, its heat distortion temperature for an A/E value of 1.05 was found to be 210 and for an A/E value of 1.25 it was found to be 210.

Examples 8 and 9 indicate that the anhydride used therein was more effective when used with the Epoxide 201 than when used with Epon 828.

It can thus be seen that a convenient and economical means has been provided whereby epoxy resin systems characterized by extremely high distortion temperature characteristics are obtained. Although certain preferred embodiments of the invention have been disclosed for purposes of illustration, it will be evident to those skilled in this art that various changes and modifications can be made therein without departing from the scope and spirit of the invention.

The polymerizable epoxy resin compositions which are cured by practicing the principles of this invention are well known in the art. As illustrated in Example 7, the dianhydride can be used to advantage with all types of epoxy resins: those in which the epoxy group is in a terminal position and those in which the epoxy group is an internal position, as for example the Epoxide 201 referred to in Example 7 or any one of the many epoxycontaining materials referred to in U.S.P. 2,949,441 under the headings of epoxidized esters of the polyethylenically unsaturated monocarboxyli c acids, epoxidized esters of unsaturated monohydric alcohols and polycarboxylic a-cids, epoxidized esters of unsaturated alcohols and unsaturated carboxylic acids, epoxidized derivatives of polyethylenically unsaturated polycarboxylic acids, epoxidized polyesters obtained by reacting an unsaturated polyhydric alcohol and/or unsaturated polycarboxylic acid or anhydride and epoxidized polymers and polymers of diolefins such as butadiene. The specific position of the epoxy group is not a controlling feature. Such compositions, per se, constitute no part of the invention. Further, it is common practice in this art to include various auxiliary materials such as reinforcing materials, inert powders and fillers, pigments, auxiliary catalyst extenders and the like in the resin composition.

While certain theoretical explanations have been resorted to in the specification for the purpose of clarification, it should be distinctly understood that applicants are not bound by the ultimate correctness of these theories.

We claim:

1. A cured resin composition comprising an epoxy resin containing oxirane groups cured with a dianhydride having the formula:

R C-CH-C A.

I C Ha-C in which are alkylidene radicals each containing 2 to 6 carbon atoms and R represents 4 nuclear substituents each selected from the group consisting of hydrogen and C -C alkyl radicals, said dianhydride being present in an amount to provide a ratio of at least 0.6 of anhydride equivalents epoxy equivalents.

2. A cured resin composition comprising an epoxy resin containing oxirane groups cured with phenylenebis-(3-butane-1,2-dicarboxylic acid anhydride), said anhydride being present in an amount to provide a ratio of at least 0.6 of anhydride equivalent:epoxy equivalents.

3. A cured resin composition comprising an epoxy resin containing oxirane groups cured with phenylene-bis- (3-methyl-3-butane-1,2-dicarboxylic acid anhydride), said anhydride being present in an amount to provide a ratio of at least 0.6 of anhydride equivalentzepoxy equivalents.

4. The process for curing an epoxy resin which comprises forming a mixture comprising an epoxy resin containing oxirane groups and a dianhydride curing agent for epoxy resins having the formula:

are alkylidene radicals each containing 2 to 6 carbon atoms and R represents 4 nuclear substituents each selected from the group consisting of hydrogen and C -C alkyl radicals, said dianhydride being present in an amount to provide a ratio of at least 0.6 of anhydride equivalentzepoxy equivalents, and curing the mixture at temperatures in the range between about C. and about 250 C.

5. The process for curing an epoxy resin which comprises forming a mixture comprising an epoxy resin containing oxirane groups and phenylene-bis-(3-butane-1,2- dicarboxylic acid anhydride) in such proportion that the ratio of anhydride equivalentzepoxy equivalents is at least 0.6 and curing the mixture at temperatures in the range of about 150 C. to about 250 C.

6. The process for curing an epoxy resin which comprises forming a mixture comprising an epoxy resin containing oxirane groups and phenylene-bis-(3-methyl-3- butane-1,2-dicarboxylic acid anhydride) in such proportion that the ratio of anhydride equivalentzepoxy equivalents is at least 0.6 and curing the mixture at temperatures in the range of about 150 C. to about 250 C Lee et al., Epoxy Resins, pages '15 and 128 relied on, McGraw-Hill Book Co., Inc., New York, 1957.

WILLIAM H. SHORT, Primary Examiner. T. D. KERWIN, Assistant Examiner. 

1. A CURED RESIN COMPOSITION COMPRISING AN EPOXY RESIN CONTAINING OXIRANE GROUPS CURED WITH A DIANHYDRIDE HAVING THE FORMULA: 